CN101868762A - Photopatternable deposition inhibitor containing siloxane - Google Patents

Photopatternable deposition inhibitor containing siloxane Download PDF

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Publication number
CN101868762A
CN101868762A CN200880116804A CN200880116804A CN101868762A CN 101868762 A CN101868762 A CN 101868762A CN 200880116804 A CN200880116804 A CN 200880116804A CN 200880116804 A CN200880116804 A CN 200880116804A CN 101868762 A CN101868762 A CN 101868762A
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deposition
deposition inhibitor
light
patternization
inhibitor material
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CN101868762B (en
Inventor
L·M·欧文
D·H·莱维
D·C·弗里曼
C·杨
P·J·考德里-科万
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Eastman Kodak Co
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Eastman Kodak Co
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0754—Non-macromolecular compounds containing silicon-to-silicon bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Vapour Deposition (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

An atomic-layer-deposition process for forming a patterned thin film comprising providing a substrate, applying a photopatternable deposition inhibitor material to the substrate, wherein the deposition inhibitor material comprises an organosiloxane compound; and patterning the deposition inhibitor material. The thin film is substantially deposited only in the selected areas of the substrate not having the deposition inhibitor material.

Description

But the light pattern deposition inhibitor that contains siloxane
Technical field
The present invention relates to form the method for patterning (patterned) film by the constituency deposition.Particularly, but the present invention relates to adopt the organic siloxane compound that contains light patternization method as the deposition inhibitor compound compositions.
Background technology
Modern electronic equipment needs the electricity or the light active material layer of a plurality of patternings, is sometimes on bigger base material (substrate).Electronic equipment such as radio-frequency (RF) identification (RFID) label, photoelectricity, light and chemical sensor all needs the patterning of certain level in its electronic circuit.Flat-panel monitor, the sequence layer that depends on precise patterning as LCD or electroluminescent display (for example OLED) forms the backboard thin-film component.These elements comprise capacitor, transistor and power bus.In order to promote performance and to reduce cost, the inherent new method of constantly exploring material deposition and layer patternization of industry.
Thin film transistor (TFT) (TFT) can be counted as the representative of the electronics and the manufacturing issue of many thin-film components.TFT is at electronic equipment, for example active matrix (active-matrix) LCD, smart card and various other electronic device and parts thereof, in be widely used as on-off element.Thin film transistor (TFT) (TFT) is an example of field effect transistor (FET).The most famous example of FET is a MOSFET (metal-oxide semiconductor (MOS)-FET), be used for the ordinary tap element of high-speed applications now.For the application that transistor need be applied on the base material, generally use thin film transistor (TFT).The committed step of making thin film transistor (TFT) relates to semiconductor deposition to base material.At present, most of thin-film devices are to use vacuum-deposited amorphous silicon as semiconductor, adopt conventional photoetching process to be patterned, and make.
Amorphous silicon is used for TFT as semiconductor and still has its defective.When making transistor, the deposition of amorphous silicon needs relative difficult or complicated method to realize electrical characteristics enough for display application as plasma enhanced chemical vapor deposition and high temperature (360 ℃).The feasible deposition that can not be implemented on the base material of making by some plastics of this high treatment temperature, and described plastics may be expected for the application such as flexible display.
People are increasing to the semi-conductive interest of deposit film on plastics or flexible parent metal, particularly because higher, the weight of these carrier physical strengths is light and, for example, make it possible to achieve more economical manufacturing by allowing to adopt volume to volume (roll-to-roll) technology.A useful example of flexible parent metal is a polyethylene terephthalate.Yet these class plastics are being lower than 200 ℃ with the device treatment limits.
Although flexible parent metal has potential advantage, but exist many and the carrier related problem of plasticity when in conventional manufacture process, adopting traditional photoetching process, make to be difficult to reach the arrangement (alignment) of the enterprising row transistor element of typical substrates more than 1 meter or 1 meter at width.Maximum treatment temperature, solvent resistance, dimensional stability, water and the solvent swell of base material may have a strong impact on traditional photoetching process and equipment generation, and all key parameters of plasticity carrier are usually all not as good as glass.
The low-cost depositing operation that does not relate to the expense relevant with subraction patterning (subtractive patterning) technology with application of vacuum is adopted in interesting also having.In typical vacuum technology,, need big metallic room and complicated pumped vacuum systems for necessary environment is provided.In typical subraction patterning system, the most of material that deposits in vacuum chamber all for example in etching step, is removed.These deposition and patterning method cost of investment height, the convenient of also having got rid of based on the continuous volume width of cloth (continuous web) of system uses.
In the past during the decade, there are many materials to cause people's attention as the possible substitute of the amorphous silicon of the semiconductor channel that is used for thin film transistor (TFT).The semiconductor material that is easy to process is desirable, and particularly those can be applied to semiconductor material on the large tracts of land by better simply technology.Can will open the substrate material of the more wide region that comprises plastics for flexible electronic devices at the semiconductor material of lower temperature deposition.The dielectric material that is easy to process with patterning also is a key low-cost and that flexible electronic devices successfully realizes.
For present silicon-based technologies finds practical inorganic semiconductor substitute also is the target of many research work.For example, known have a metal-oxide semiconductor (MOS), and the commonplace indium zinc of zinc paste, indium oxide, oxidation, tin oxide or the cadmium oxide of other doped chemical of metal such as aluminium arranged or do not comprise when comprising deposition.As described below, the transparent semiconductor material of this class has extra advantage for some is used.In addition, metal-oxide dielectric such as aluminium oxide (Al 2O 3) and TiO 2In the electronic application of reality and optical application such as interference filter also of great use.
Many device architectures can use aforesaid functional layer to make.Dielectric is placed between two conductors can obtains capacitor.The semiconductor of two complementary bearer types is placed between two conductive electrodes can obtains diode.Also can have intrinsic semiconductor regions between the semiconductor of described complementary bearer type, promptly this district has low free charge carrier number.Also can construct diode by single semiconductor is placed between two conductors, one of them conductor/semiconductor interface produces the strong Schottky barrier that stops electric current in one direction.Place insulation course by going up, then place semi-conductive layer and can obtain transistor at conductor (grid).If (spaced apart) contacts with described top semiconductor layer two or more extra conductor electrodes (source and drain electrode) are set diffusedly, can form transistor.As long as generated crucial interface, can generate any above-mentioned device with various configurations.
People are more and more interested in the technology that is known as constituency deposition or SAD.As its name suggests, the constituency deposition relates to certain (a bit) of handling base material thereby material only is deposited on the zone those expectations or that select.For example; people such as Sinha (J.Vac.Sci.Technol.B2462523-2532 (2006)) have mentioned; constituency ALD (ald) requires the appointed area on surface covered or " protection " gets up preventing that the ALD reaction takes place in these constituencies, thereby guarantees nucleation and the growth on the zone do not covered that the ALD film is only being expected.The constituency that can also adopt surf zone wherein by " activation " thereby or surperficial being modified make film only be deposited over SAD technology on the described activating area.The constituency sedimentation has many potential advantages, has for example eliminated the etching process that is used for film patterning, has reduced required cleaning number of times, and can be difficult to etched material by patterning.Conley, people's such as Jr. denomination of invention is to have introduced a kind of method that combines patterning and deposited semiconductor in the U.S. Pat 7,160,819 of " METHOD TO PERFORMSELECTIVE ATOMIC LAYER DEPOSTION OF ZINC OXIDE ".Conley, people such as Jr. have discussed and have been used in the material that silicon wafer (silicon wafer) is gone up patterning zinc paste.But do not provide the relevant information of using the result of other base material or relevant other metal oxide.
There are many materials to be studied guiding inhibitor (directorinhibitor) compound of personnel as the constituency deposition.People such as Sinha above the reference, have used poly-(methyl methacrylate (PMMA) in their mask layer.Conley, people such as Jr. used acetone and deionized water together with other process contaminants as the deposition inhibitor material.The problem of these previously used guiding inhibitor is that they are only effective to the thin material that guiding is selected.In addition, in order to can be used for constructing device, need be to guiding inhibitor compound patterning in addition.Other method of patterning guiding inhibitor such as lithography or ink-jet are subject to its resolution.Equally, existence can not be by the difficulty of the different layers in the independent location resulting devices that solves of constituency deposition.Therefore exist can be used for series of thin membrane material, patterning and being suitable for easily with the plain mode needs of the guiding inhibitor compound of patterning highly precisely.
Summary of the invention
But the present invention relates to be used for the light pattern guiding inhibitor material of gas-phase deposition.This method that is used to form patterned film comprises:
(a) provide base material;
(b) but on base material, apply the composition of the deposition inhibitor material that comprises light patternization, wherein said deposition inhibitor material includes organic siloxane;
(c) but the deposition inhibitor material of light patternization is exposed to the imaging actinic radiation to form the pattern that is made of the deposition inhibitor material that is in the second exposure attitude, the wherein said second exposure attitude is different from first and applies attitude;
(d) but the deposition inhibitor material of the light patternization by handling described exposure with the deposition inhibitor patterns of materialization, so that the constituency that does not in fact have the deposition inhibitor material to be provided; With
(e) on base material, deposit the functional material layer by gas-phase deposition;
Wherein functional material only is deposited in the constituency that does not have the deposition inhibitor material on the base material basically.Should be understood that, but any CVD (Chemical Vapor Deposition) method all can be used for the deposition inhibitor material of described light patternization.
An advantage of the present invention is can selective deposition metal oxide and other material.
Another advantage of the present invention is to comprise the deposition on large area substrates applicable to the deposition on the volume width of cloth or other moving substrate.
Another advantage of the present invention is that in preferred embodiments, it makes and can work under atmospheric pressure.
Another advantage of the present invention is to can be used for the low temperature process under the atmospheric pressure, and this technology can be in blow-by, implement under the environment of atmosphere opening.
After the reference accompanying drawing is read following detailed description the in detail, one of ordinary skill in the art can know purpose of the present invention, feature and advantage, wherein demonstration and described illustrative embodiment of the present invention in the accompanying drawing.
Description of drawings
Although specifically note and clearly claimed theme of the present invention with this instructions that claim finishes, believe that the present invention may be better understood with reference to accompanying drawing by following explanation, wherein:
Figure 1A-1E has shown the layer on the difference place of technology base material in one embodiment of the invention;
Fig. 2 is the process flow diagram of an embodiment of processing step of the present invention;
Fig. 3 is the side cross-sectional view of precipitation equipment that is used for an embodiment of the inventive method, in one embodiment, has shown to offer the gaseous material configuration that stands the base material that thin film deposition processes described in the embodiment handles; With
Fig. 4 is the side view that is used for to the gas supply device of the precipitation equipment supply gas of Fig. 3, has shown the gaseous material configuration that offers the base material that stands PROCESS FOR TREATMENT described in the embodiment.
Detailed description of the invention
The present invention relates to adopt constituency deposition (SAD) to form the film of patterning.Can adopt various CVD (Chemical Vapor Deposition) method to deposit described film, for example chemical vapor deposition (CVD) or ald (ALD).Constituency deposition, as mentioned above, relate to certain (a bit) of handling base material thus partly material only is deposited in those desired region.But the present invention adopts the deposition inhibitor material that can suppress thin film deposition light patternization in its surface.Mode thus exists the part of deposition inhibitor material will have only seldom to the film growth that does not have degree, and will have normal film growth in the substrate regions that does not generally contain described inhibitor material on the base material.
Term " deposition inhibitor material " in this article refers at the material that is applied to by gas-phase deposition on the base material, perhaps comes from any randomly crosslinked subsequently material that maybe can carry out other reaction of modification to the material that just may exist before the deposition inorganic thin film.
But the present invention relates to organosiloxane as the application of the deposition inhibitor material of light patternization with include the preparaton of organic siloxane.Organosiloxane is commonly defined as and is included in the compound that consists essentially of the skeleton that alternately is made of Si and O atom or part in its chemical constitution, and wherein each side at-O-Si-O repetitive all has at least one, preferably two organic groups are connected on the Si atom.Described organic group can have various substituting groups such as halogen, comprises fluorine.Most preferably, described organic group is to be substituted independently or the unsubstituted 1-6 of a having carbon atom, preferably alkyl, phenyl or the naphthenic base of 1-3 carbon atom, preferably replaces or unsubstituted methyl.
Organic siloxane polymer is defined as and comprises polymkeric substance, prepolymer or macromonomer.Particularly preferably be on being applied to base material and, be insoluble deposition inhibitor material through after any crosslinked or intermolecular reaction.This class organic siloxane polymer comprises random or block and/or cross-linked polymer.Can utilize after being applied to organic siloxane polymer on the substrate surface that crosslinked that it is become is insoluble.Described crosslinked can the generation in the patterning process to help this patterning step for example by adopting the crosslinked and patterning that carries out that is caused by actinic radiation, succeeded by removing no cross-linked polymer, for example passed through solvent.
Randomly, on organic siloxane polymer, can there be functional group, as end group (being also referred to as END CAPPED GROUP).Also can there be crosslinkable groups and/or functional group, for example be present on the outer side chain of siloxane main chain.
The example of organic siloxane polymer comprises that for example, poly-(alkylsiloxane), poly-(aryl siloxanes), poly-(alkylaryl siloxane) and poly-(alkyl (aryl) siloxane) preferably have functional group.Gather (siloxane) that this type of is functionalized comprises epoxy-functional, carboxy-functionalized, Polyetherfunctionalization, that phenol is functionalized, aminofunctional, alkoxy-functionalization, poly-(organosiloxane) that methacryl is functionalized, that methyl alcohol is functionalized, hydroxy-functional, vinyl-functional, acrylic acid functionalized, silane-functionalised, that trifluoro is functionalized or hydrosulphonyl functionalized.If at least one block contains considerable siloxane repeat unit, so also can use segmented copolymer.Described polymkeric substance can be prepared described in many patents and publication, also can be commercially available from for example General Electric, Dow Corning and Petrarch.
Preferred poly-(organosiloxane) polymkeric substance comprises random or segmented copolymer, comprises to be the organic group of following group (being connected on the silicon atom) independently: hydrogen has the alkyl of 1-18 carbon, as methyl, ethyl, propyl group, butyl etc.; Have 6-18 carbon, the aryl of 6-8 carbon atom preferably, as phenyl, benzyl, naphthyl etc.; Mercaptoalkyl with 1-18 carbon is as dredging basic propyl group; Aminoalkyl with 1-18 carbon is as aminopropyl or amino isopropyl; Trifluoroalkyl with 1-18 carbon is as trifluoromethyl; Or have three fluoro aryls of 6-18 carbon, as trifluoromethyl.The preferable weight-average molecular weight scope of poly-(organosiloxane) polymkeric substance if do not have crosslinkedly, is 200-140,000, more preferably 4, and 000-120,000.Preferably, alkyl has 1-6 carbon atom, more preferably 1-3 carbon atom.
Some preferred illustrative poly-(organosiloxane) polymkeric substance (or its major part) are poly-(dimethyl siloxane), poly-(diphenyl siloxane), poly-(methyl phenyl siloxane), poly-(dimethyl diphenyl siloxane), dredge basic propyl group functionalized poly-(dimethyl siloxane), poly-(dimethyl siloxane) that aminopropyl is functionalized, poly-(dimethyl siloxane) that the carboxylic propyl group is functionalized, poly-(dimethyl siloxane) that silane-functionalised poly-(dimethyl siloxane) and trifluoro propyl are functionalized.Preferred poly-(organosiloxane) polymkeric substance for poly-(dimethyl siloxane) (PDMS) and poly-(dimethyl diphenyl siloxane), that is to say that wherein organic group suitably is a methyl or phenyl.Can use the potpourri of poly-(organosiloxane) polymkeric substance or compound.As follows, organosiloxane can be according to circumstances with other polymer mixed.
Different with other deposition inhibitor material, the organosiloxane that is used for constituency deposition (SAD) can provide on the inhibitor surface near zero film growth.This characteristic has improved the practicality of deposition inhibitor material greatly, has film than the much bigger thickness that can deposit in the past because it makes it possible to selective deposition in SAD technology.
In one embodiment of the invention, by gas-phase deposition, as ALD, deposition also uses constituency deposition (SAD) material and technology to carry out the film that patterning has obtained patterning simultaneously.SAD technology has been used the deposition inhibitor compound, to suppress the film ALD growth in the non-election district.
ALD can be used as the manufacturing step of the film that forms many types of using in the electronic devices and components, and described electronic devices and components comprise semiconductor devices and support (supporting) electronic devices and components such as resistor and capacitor, insulator, bus and other conductive structure.ALD is specially adapted to form the thin layer of metal oxide in the electronic device element.Can utilize several big class functional material of ALD deposition to comprise conductor, dielectric or insulator and semiconductor.
Advantageously, the ALD step be stop voluntarily and can proceed to or surpass when stopping exposure time voluntarily atomic layer of deposition just.Atomic layer is generally 0.1-0.5 molecular monolayer, and typical sizes approximately is no more than several dusts.In ALD, the deposition of atomic layer is the result of the chemical reaction between reactive molecule precursor and the base material.In the ALD of each separation reactive deposition step, the atomic layer of clean reactive deposition expectation and eliminating basically was included in the described molecular precursor originally " extra " atom.In its most simple form, ALD relates to absorption and the reaction of each precursor under the situation of other one or more precursors that do not have reaction fully.In fact in any technology, all be difficult to avoid cause some direct reaction of the different precursors of a spot of chemical vapour deposition reaction.The target of declaring to carry out any technology of ALD all is to obtain the device performance and the attribute that match with ALD technology when admitting to allow a spot of CVD reaction.
In ALD uses, be typically in the stage of separating and in the ALD reactor, introduce two kinds of molecular precursor.For example, metal precursor molecule ML xComprise the metallic element M that is combined on atom or the molecule ligand L.For example, M can be but be not limited to Al, W, Ta, Si, Zn etc.When having prepared substrate surface when can directly react, metal precursor and base material reaction with molecular precursor.For example, prepare substrate surface usually so that it comprise can be with the hydrogeneous ligand AH of metal precursor reaction etc.Some typical A thing classes comprise sulphur (S), oxygen (O) and nitrogen (N).All ligands on gaseous precursors molecule and the substrate surface are reacted effectively, cause the deposition of metal monoatomic layer:
Base material-AH+ML x→ base material-AML x-1+HL (1) wherein HL is a byproduct of reaction.In course of reaction, initial surface coordination body AH is consumed, the surface become by can not with metal precursor ML xThe AML of further reaction X-1Ligand covers.Therefore, when lip-deep all initial AH ligands all by AML X-1Reaction stops voluntarily during replacement.In inert gas purge stage normally after this stage of reaction, it removed unnecessary metal precursor and HL accessory substance from the chamber before other precursor is introduced separately into.
Use second kind of molecular precursor to recover the surface reaction of base material then to metal precursor.This is for example by removing described L ligand and redeposited AH ligand is finished.In this case, this second precursor generally includes expectation (normally nonmetallic) elements A (being O, N, S) and hydrogen (is H 2O, NH 3, H 2S).Ensuing reaction is as follows:
Base material-A-ML+AH Y→ base material-A-M-AHL+HL (2)
This can change back to the state that its AH covers to the surface.(here, for simplicity, described chemical reaction is not a balance).The extra elements of expectation, A is introduced in the film, and the ligand of not expecting, L is used as volatile byproducts and removes.Equally, described reaction consumes reactive site (this time being the position of described L end-blocking) and the active site on base material stop voluntarily when being exhausted fully.From the settling chamber, remove described second molecular precursor in second purge stages by the inert purge gas that flows then.
In a word, ALD arts demand sequence alternate chemicals is to the flux (flux) of base material.As mentioned above, representational ALD technology is the circulation with four different operating stages:
1.ML xReaction;
2.ML xPurge;
3.AH yReaction; With
4.AH yPurge, get back to the stage 1 then.
The surface reaction alternately and precursor that substrate surface returns to its initial reaction sexual state removed this repetitive sequence, and the purge operations of inserting are exactly typical A LD deposition cycle.A key feature of ALD operation is that base material is returned to its initial surface chemistry state.The step of using this group to repeat, can with film with at measuring layer stratified sedimentation such as all identical aspect chemical kinetics, each round-robin deposition, composition and the thickness to base material.
The self-saturation surface reaction makes ALD insensitive to the migration unevenness, otherwise because the restriction of engineering tolerance and line production or because surface topography (that is, in structural deposition three-dimensional, high aspect ratio), this will diminish surface uniformity.Generally, the inhomogeneous flux of chemicals can cause different deadlines in zones of different usually in course of reaction.Yet, adopt ALD, make each reaction on whole substrate surface, to finish.Thus, finishing dynamic (dynamical) difference does not hinder homogeneity.This is to have stopped reaction voluntarily because at first finish the zone of reaction; Other zone can be continued, and has all carried out the reaction of expection until the surface that entire process is crossed.
Generally, the ALD technology film of deposition 0.1-0.2nm in (as top listed step 1-4) that circulates at single ALD.For provide for many or most of semiconductor application the homogeneous thickness of 3nm-300nm scope and for other is used thicker thickness, must realize useful and economically viable cycling time.The industrial capacity standard code this means that to base material treatment 2 minutes-3 minutes ALD cycling time must be 0.6 second-6 seconds scope.
ALD technology must be efficiently and is carried out many circulations of this sequence reliably so that can apply many base materials effectively by cost.Be reflected at the required time that stops voluntarily that arrives under any given temperature of reaction in order to minimize ALD, a kind of method is to use so-called " pulse " technology to make the flux maximization of the chemical flow that enters the ALD reactor.In pulse ALD technology, base material is arranged in indoor and by making first gas enter described chamber, then remove described gas, introduce second gas, remove described second gas in pumping circulation again and be exposed to the above-mentioned gas sequence to described chamber then in pumping circulation.This sequence can be come repetition with any frequency and gas type and/or concentration change.Clean effect is that whole chamber experiences gas composition over time, and this class ALD can be known as (time dependent) ALD of time correlation thus.The ALD that most existing ALD technologies all are time correlations.
For the inherent limitations of the ALD system that overcomes time correlation, can provide continuously every kind of reacting gas simultaneously moving substrate make it pass every kind of gas successively.In these systems, have relatively-stationary gas composition, but it is fixed in the specific region or the space of disposal system.These systems can be known as space correlation (spatially dependent) ALD system.
For example, the denomination of invention of Yudovsky is the U.S. Pat 6 of " GAS DISTRIBUTION SYSTEMFOR CYCLICAL LAYERD EPOSITION ", 821,563 have recorded and narrated a kind of ALD disposal system of space correlation, under vacuum, gas ports with precursor and purge gas of separation, and the vacuum pump port between each gas ports is alternately.Each gas ports is with its air-flow base material that leads vertically downward.Wall or dividing plate are separated described air-flow, and are useful on the vacuum pump of exhaust in the both sides of each air-flow.People's such as Suntola denomination of invention is the another kind of method that discloses the ALD of the space correlation of using continuous flow in the U.S. Pat 4,413,022 of " METHOD FOR PERFORMING GROWTH OF COMPOUND THINFILMS ".The air-flow array has source gas openings, vector gas opening and vaccum exhaust outlet alternately.The to-and-fro movement of base material on described array realizes the ALD deposition, do not need pulse operation.
The U.S. Patent Publication 2005/0084610 of Selitser discloses a kind of atmospheric pressure atomic layer chemical vapor deposition technology.Selitser thinks that the thundering increase of reaction rate realizes by working pressure being become atmospheric pressure, and this will make reactant concentration be order of magnitude increase, thereby surface reaction thing ratio is improved.
The ALD technology of space correlation can be used the U.S. Patent Publication of transferring the possession of common 2007/0238311; U.S. Patent Publication 2007/0228470; U.S. Patent Publication 2008/0166884 and U.S. Patent application No.11/620, in 744 other device or the system recorded and narrated in detail finish.These systems are a difficult point that overcomes the ALD system of space correlation, i.e. effort has been made in the mixing of not expecting of the reacting to each other property gas of continuous flow.Particularly, U.S. Patent Publication 2007/0238311 has adopted new cross flow pattern to prevent to mix, and U.S. Patent application 11/620,744 has adopted the dispense tip that is floated by the pressure portion of the reactant gas in the technology to realize that improved gas separates with U.S. Patent Publication 2008/0166884.
Although ALD is the method that preferably deposits the functional material layer, those of ordinary skills will be understood that also can use other common CVD (Chemical Vapor Deposition) method.
Method of the present invention can be better understood with reference to Figure 1A-1E.Figure 1A has shown the base material 200 before applying deposition inhibitor material 210.Although base material 200 is illustrated as naked base material, those of ordinary skills should be understood that, base material 200 can, as required, comprise the patterning that is used for any electricity, optics or mechanical purpose or the material layer of patterning not.Figure 1B has shown at uniform deposition the base material 200 after the deposition inhibitor material 210.Fig. 1 C has shown the base material 200 after the step that deposition inhibitor material 210 is patterned to deposition mask 225.Described patterning can adopt any method known in the art to finish, and comprises the photoetching process, laser ablation or other subraction that use positivity or negative-working photoresist.As shown in the figure, deposition mask 225 comprises deposition inhibitor material area 210 and no deposition inhibitor zone 215.Fig. 1 D illustration the base material 200 after the step of the membraneous material of ald expectation.As shown in the figure, 220 of membraneous materials are deposited on the place that does not have deposition inhibitor material 210 on the base material 200.On deposition inhibitor material 210, membraneous material 220 does not form any perceptible film.Fig. 1 E illustration the membraneous material 220 of the patterning after removing deposition inhibitor material 210.One skilled in the art should be understood that, are not essential removing deposition inhibitor material 210 in some cases.
Fig. 2 is the block diagram of an embodiment of the inventive method, has wherein used the combination of constituency deposition (SAD) and ALD to make patterned film.As shown in the figure, in step 100, base material is supplied in the system.In step 105, but the deposition inhibitor material of deposition light patternization.But the deposition inhibitor material of described light patternization can be to cause material to deposit any material of repressed available light patterning usually.In one embodiment, but the deposition inhibitor material of described light patternization select for treating that deposition materials is special.In other embodiments, described deposition inhibitor material has given restraint (inhibition power); Described restraint is defined in and is less than or equal to the effective bed thickness of deposition inhibitor material at that time.In other embodiments, but the deposition inhibitor material of light patternization only be chosen as selected visible wavelength sensitivity.But the conforming layer of the deposition inhibitor material of step 105 deposition light patternization, step 110 is used to form the deposition inhibitor material layer of patterning.Step 110 comprises the step that but the deposition inhibitor material of light patternization is exposed to light pattern.Described exposure can use the big light source that passes traditional mask or color mask to finish, and perhaps, but also can use laser marking system to come the deposition inhibitor material of light patternization is exposed.For mask exposure, described mask can contact with base material also can focus on base material by scioptics.Mask exposure can be finished by single on whole base material, and perhaps mask also can be that (stepped) of stepping is to realize exposure for several times on base material.But step 110 also comprises the deposition inhibitor material step of developing with light patternization, thereby base material is had do not exist the zone of deposition inhibitor material and kept the zone of deposition inhibitor material.
Continuation is with reference to Fig. 2, and step 120 has deposited the film of expectation by gas-phase deposition.In a preferred embodiment, described gas-phase deposition is ald (ALD) technology.General this deposition can be used any suitable ALD equipment, preferably the relevant ALD system of usage space.Film only is deposited on the zone that does not have the deposition inhibitor material on the base material.According to used film, the deposition inhibitor material can be retained in and be used for following process on the base material and also can be removed shown in the step 130 of Fig. 2.
But the present invention has used the deposition inhibitor material of the light patternization that includes organic siloxane.Can pass through long UV or visible light patternization for making, but described light pattern deposition inhibitor also comprises sensitizer (sensitizer).
Deposition inhibitor material of the present invention preferably has effective restraint, and restraint is defined in and is less than or equal to the effective functional layer thickness of deposition inhibitor material at that time.Preferably, the deposition inhibitor material shows at least 50 in use , more preferably at least 100
Figure GPA00001139253700112
, most preferably at least 300
Figure GPA00001139253700113
Restraint.
Organosiloxane can be crosslinked after applying or photopolymerization.Can utilize after being applied to polymer deposition inhibitor material on the substrate surface that crosslinked that it is become is insoluble.Described crosslinked can in the patterning process, the generation promoting this patterning step, but for example by adopting,, for example pass through solvent succeeded by removing non-cross-linked polymer by cause crosslinked of the deposition inhibitor that exposes light patternization and the patterning that carries out.
But the material that except that organosiloxane, also comprises light patternization in the deposition inhibitor material, but for example photopolymerization or light the dissolving material, with the combination of sensitization system, this combination is known as the photopolymerization system, thereby it can obtain the deposition inhibitor material with the organosiloxane blend.
Known have various photopolymerization systems that visible light or non-visible light radiation trigger of passing through that can be used for method of the present invention.At " the PhotoreactivePolymers:The Science and Technology of Resists " that A.Reiser delivers, Wiley-Interscience, John Wiley ﹠amp; Sons, 1989, the 102-129 page or leaf, the U.S. Pat 4 of Farid, 859, but in 572 relevant for the useful discussion of UV curing and visible light light pattern formed material, but wherein recorded and narrated a kind of light pattern formed material of the imaging system that is used to take a picture, it depends on and uses harden organic component and produce image graphics of visible light.This list of references been has also has been recorded and narrated the various suitable light trigger to the visible light sensitivity, monomer and the film formulation criterion that is used for cured layer, and wherein said cured layer can be used from method of the present invention with organosiloxane one.
The sensitization system that is used for the photopolymerization system is used to provide the light sensitivity to visible light (sensitivity), can pass through practical photo-induced polymerization initiator (together with polymerisable compound) and realize.In a preferred embodiment of the invention, but but the light pattern formed material that is used for the deposition inhibitor material of light patternization comprise to be selected from and have at least one, preferably have the polymerizable compound of the compound of two or more ethylenic unsaturated links at least.This compounds is well known in the art, and they can not have particular restriction ground to be used for the present invention.The chemical species of this compounds can be for example monomer, prepolymer (being dimer, tripolymer) and oligomer or potpourri and their multipolymer.As the example of monomer whose and multipolymer, unsaturated carboxylic acid (for example acrylic acid, methacrylic acid, itaconic acid are arranged; Crotonic acid, iso-crotonic acid, maleic acid etc.) and ester and acid amides, the ester of unsaturated carboxylic acid and aliphatic polyol compound and the acid amides of unsaturated carboxylic acid and aliphatics polyhydroxy amine compound preferably used.In addition, also preferably use to have the esters of unsaturated carboxylic acids of nucleophilic displacement of fluorine base such as hydroxyl, amino and sulfydryl and the addition reaction product of acid amides and simple function or polyfunctional isocyanate and epoxy material class (epoxies), and the dehydration condensation product of these compounds and simple function or polyfunctional carboxylic acids.Also preferably use to have the esters of unsaturated carboxylic acids of electrophilic substituent such as isocyanate group and epoxy radicals and acid amides and simple function or polyfunctional alcohol's addition reaction product, and have the esters of unsaturated carboxylic acids of releasable substituting group such as halogen and tolysulfonyl oxygen base and the substitution reaction product of acid amides and simple function or polyfunctional alcohol, amine and mercaptan.As another example, also can use the compound that replaces with unsaturated phosphonic acids, styrene, vinethene etc., rather than above-mentioned unsaturated carboxylic acid.
The object lesson of the ester monomer of aliphatic polyol compound and unsaturated carboxylic acid class comprises, as acrylate, glycol diacrylate, triethylene glycol diacrylate, 1, the 3-butanediol diacrylate, 1, the 4-butanediol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloyl-oxy propyl group) ether, the trimethylolethane trimethacrylate acrylate, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the dipentaerythritol diacrylate, dipentaerythritol acrylate, the D-sorbite triacrylate, the D-sorbite tetraacrylate, D-sorbite five acrylate, D-sorbite six acrylate, three (acrylyl oxy-ethyl) isocyanuric acid ester, polyester acrylic ester oligomer or the like.As methacrylate, example comprises 1, the 4-butanediol dimethylacrylate, triethylene glycol dimethacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, the trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, the 1,3 butylene glycol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylate, the dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylate, the D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylate and two [right-(3-methacryloxy-2-propoxyl) phenyl] dimethylmethane, two [right-(methacryl ethoxy)-phenyl] dimethylmethane.As itaconate, example comprises ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate (1,4-butanediol diitaconate), 1,4-butylene glycol diitaconate (tetramethylene glycol diitaconate), pentaerythrite diitaconate and D-sorbite four itaconates.As crotonates, example comprises ethylene glycol bisthioglycolate crotonates, 1,4-butylene glycol two crotonatess, pentaerythrite two crotonatess and D-sorbite four crotonatess.As the iso-crotonic acid ester, example comprises ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters and D-sorbite four iso-crotonic acid esters.As maleate, example comprises ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate and D-sorbite four maleates.In addition, also can use the potpourri of above-mentioned ester monomer.In addition, the object lesson of the amide monomer of aliphatics polyhydroxy amine compound and unsaturated carboxylic acid comprises methylene-bisacrylamide, di-2-ethylhexylphosphine oxide Methacrylamide, 1,6-hexa-methylene bisacrylamide, 1, the two Methacrylamides of 6-hexa-methylene, diethylene triamine three acrylamides, xylylene bisacrylamide and the two Methacrylamides of xylylene.
In addition, but but the urethane ester group addition polymerizable compound that the addition reaction by isocyanates and hydroxyl obtains also can be used on the light pattern formed material of the deposition inhibitor material that is used for light patternization.An object lesson is the vinyl urethane compounds that has two or more polymerizable vinyl in a molecule, and it obtains to the addition of the polyisocyanate compound that has two or more isocyanate group in a molecule by the vinyl monomer with hydroxyl by following formula (V) expression.
CH 2=C (R) COOCH 2CH (R ') OH wherein R and R coughs up from representing H or CH 3
Other example comprises multi-functional acrylate and methacrylate, as polyester acrylate and the epoxy acrylate by epoxy resin and the reaction of (methyl) acrylic acid are obtained.In addition, also can use Sartomer Company Inc. (1999) listed photocurable monomer and oligomer in the Sartomer products catalogue.
But, can use to have the addition polymerizable compound that is fit to of desired structure and amount or the combination of addition polymerizable compound according to the final design characteristics of the deposition inhibitor material of light patternization.For example, from following angle Selection condition.For photonasty speed, preferably each molecule comprises the structure of many unsaturated groups, in most cases preferably difunctional or more polyfunctional group.Promptly solidify film strength, preferably trifunctional or more polyfunctional group for improving image area.Be used in combination different functional groups quantity and can control light sensation luminosity and intensity effectively with different polymerizable groups (for example acrylate, methacrylate, distyryl compound, vinethene compound).Have the compound of macromolecule or have a compound of high hydrophobicity very outstanding aspect film speed and film strength, but may be not preferred from developing powder and the angle developer solution, separated out.But the selection of addition polymerizable compound and use for the deposition inhibitor material of light patternization in other component (for example organosiloxane, any extra binder polymer, initiating agent etc.) compatibility and with the incompatibility of after-applied functional material, be important factors.For example, sometimes by using low-purity compound or two or more combination of compounds can improve compatibility.In addition, in order to improve adhesiveness, can also select to have the compound of ad hoc structure to carrier.For the proportioning of addition polymerizable compound in photopolymerization composite, content is high more, and light sensitivity is high more.But content is excessive being separated of may causing sometimes being harmful to because the problem that the adhesion of photopolymerization composite causes (for example manufacturing fault that is caused by the transfer and the adhesion of photochromics component), and separated out from developer solution in manufacture process.The addition polymerizable compound can use separately also and can two or more be used in combination.In addition, on the basis of having considered obstruction extent of polymerization, resolution, ashing characteristic, variations in refractive index and surface attachment that oxygen causes, can select appropriate configuration, proportioning and the addition of addition polymerizable compound arbitrarily.
But the organic polymer bonding agent of a part that can randomly constitute the film-forming components of light pattern layer comprises: (1) polyester comprises those polyester based on terephthalic acid (TPA), m-phthalic acid, decanedioic acid, hexane diacid and hexahydroterephthalic acid; (2) nylon or polyamide; (3) cellulose ether and ester; (4) polyacetals; (5) average weight-average molecular weight is 4000-4,000,000 high molecular weight epoxy ethane polymkeric substance, for example poly-(ethylene glycol); (6) polyurethane; (7) polycarbonate; (8) synthetic rubber, for example dienite and multipolymer; And (9) homopolymer and multipolymer of forming by the polymerized form that contains the undersaturated monomer of ethylenic such as any different ethylenically unsaturated monomers, as polyolefin, for example tygon and polypropylene; Poly-(vinyl alcohol); Polystyrene; Poly-(acrylic acid and methacrylic acid and ester), for example poly-(methyl methacrylate) and poly-(ethyl acrylate), and multipolymer variant.Described polymerizable compound and described polymer adhesive can use jointly with the ratio that alters a great deal, and comprise polymerizable compound that accounts for film-forming components 3-97wt% and the polymer adhesive that accounts for film-forming components 97-3wt%.Although preferred, but independent polymer adhesive is not the necessary part of light pattern film, and tend to be omitted during as polymkeric substance when the photopolymerizable compound.
But can select different light triggers to be used for the deposition inhibitor material of above-mentioned light patternization.Preferred light trigger is made of organic dyestuff.
The consumption of organic dyestuff based on the gross weight of photopolymerization composite preferably in the scope of 0.1-5wt%, more preferably in the scope of 0.2-3wt%.
Described organic dyestuff as light trigger can compatibly be selected from the compound of known usually maximum absorption wavelength in the 300-1000nm scope in the present invention.The expectation dyestuff of absorption spectrum that can be by selecting to have expectation is realized ISO.In addition, also can suitably select to be used for light source such as blue light, green glow or ruddiness or infrared LED (light emitting diode), solid-state laser, OLED (Organic Light Emitting Diode) or laser instrument or the like of visual formula exposure.
Cyanine, half cyanine and merocyanine dyes that the object lesson of light trigger organic dyestuff comprises 3-coumarin ketone (ketocoumarin) compound, sulfo-pyralium salt (thiopyrylium salts), aphthothiazoles merocyanine compound, merocyanine compound and contains merocyanine dyes, the hemioxanole dyestuff of sulfo-barbiturates and have indolenine nuclear.Other example of organic dyestuff comprises the dyestuff of being recorded and narrated among Chemistry of Functional Dyes (1981, CMC Publishing Co., Ltd., 393-416 page or leaf) and the Coloring Materials (60[4], 212-224,1987).The object lesson of these organic dyestuff comprises kation methine type dye, kation carbonium dyestuff, kation quinone imines (quinoimine) dyestuff, kation indoline dyestuff and cationic styrene type dye.The example of above-mentioned dyestuff comprises ketone dyes such as coumarine dye (comprising coumarin ketone and sulfo group cumarin (sulfonocoumarin)), portion's styrene (merostyryl) dyestuff, oxonols (oxonol) dyestuff and half oxonols (hemioxonol) dyestuff; Non-ketone dyes such as non-ketone polymethin dyes, triarylmethane dye, xanthene dyestuff, anthracene dyes, rhodamine toner dyestuff, acridine dye, aniline dyes and azo dyes; Non-ketone polymethin dyes such as azomethine dyes, cyanine dye, carbonyl cyanine dye, dicarbocyanines dyestuff, three carbonyl cyanine dyes, half cyanine dye and styrene type dyestuff; Quinone imines (quinoneimine) dyestuff such as azine dye, oxazine dye, thiazine dye, quinoline dye and thiazole dye.
Preferably, the light trigger organic dyestuff is the dye of positive ion-borate anion complex that is formed by the dye of positive ion and negative ion organic borate.The dye of positive ion absorbs the light of maximum absorption wavelength in the 300-1000nm scope, and anionic borate has four R bases, and wherein three R bases are represented aryl separately, and it can have substituting group, and a R is the alkyl of alkyl or replacement.This cationoid dyestuff-borate anion complex is at United States Patent (USP): US5,112,752; 5,100,755; 5,057,393; 4,865,942; 4,842,980; 4,800,149; Open in 4,772,530 and 4,772,541.
When the dye of positive ion-borate anion complex is used as organic dyestuff in the photopolymerization composite of the present invention, do not require the use organic borate.Yet,, preferably organic borate is used in combination with the dye of positive ion-borate complex in order to increase the photopolymerization light sensitivity.Organic dyestuff can use separately also and can be used in combination.
The above-mentioned dye of positive ion-boratory object lesson is as follows.But, should be understood that the present invention is not limited in these examples.
Dyestuff-1
Figure GPA00001139253700161
Dyestuff-2
Figure GPA00001139253700171
Dyestuff-3
Figure GPA00001139253700172
Dyestuff-4
Figure GPA00001139253700173
Dyestuff-5
Figure GPA00001139253700181
Dyestuff-6
Figure GPA00001139253700182
Dyestuff-7
Figure GPA00001139253700183
Dyestuff-8
Figure GPA00001139253700184
Dyestuff-9
Figure GPA00001139253700191
Dyestuff-10
Figure GPA00001139253700192
Dyestuff-11
Figure GPA00001139253700193
Dyestuff-12
Figure GPA00001139253700201
Dyestuff-13
Figure GPA00001139253700202
Dyestuff-14
Figure GPA00001139253700203
Dyestuff-15
Figure GPA00001139253700211
Dyestuff-16
Dyestuff-17
Figure GPA00001139253700213
Dyestuff-18
Figure GPA00001139253700221
Dyestuff-19
Figure GPA00001139253700222
May be preferably with light trigger and organic borate, as in United States Patent (USP): US5,112,752; 5,100,755; 5,057,393; 4,865,942; 4,842,980; 4,800,149; Those disclosed in 4,772,530 and 4,772,541 is used in combination.During use, the amount of the borate compound in the photopolymerization composite of the present invention is 0-20wt% based on the total amount of photopolymerization composite preferably.The borate that can be used for photosensitive composition of the present invention is represented by following general formula (I).
[BR 4] -Z +Wherein the Z representative can form kation but the group of non-photosensitivity, [BR 4] -For having the borate compound of four R bases, described R base is selected from alicyclic group, the heterocyclic radical of alkynyl, alicyclic group, the replacement of thiazolinyl, alkynyl, the replacement of alkaryl, thiazolinyl, the replacement of aralkyl, alkaryl, the replacement of aryl, aralkyl, the replacement of alkyl, aryl, the replacement of alkyl, replacement, the heterocyclic radical and the derivant thereof of replacement.A plurality of R can be same to each other or different to each other.In addition, two or more these groups can directly or by substituting group combine, and form the heterocycle of boracic.Z +Absorbing light not, it represents alkaline metal, quaternary ammonium, pyridine, quinoline, diazonium, morpholine, tetrazolium, acridine, phosphine, sulfonium, oxygen sulphur, iodine, S, P, Cu, Ag, Hg, Pd, Fe, Co, Sn, Mo, Cr, Ni, As or Se.
Above-mentioned boratory object lesson is as follows.But, should be understood that the present invention is not limited in these examples.
BS-1
Figure GPA00001139253700231
BS-2
Figure GPA00001139253700232
BS-3
Figure GPA00001139253700233
BS-4
Figure GPA00001139253700234
BS-5
Figure GPA00001139253700241
BS-6
Figure GPA00001139253700242
BS-7
BS-8
BS-9
Figure GPA00001139253700251
BS-10
Figure GPA00001139253700252
BS-11
Figure GPA00001139253700253
BS-12
Figure GPA00001139253700254
BS-13
Figure GPA00001139253700255
BS-14
Figure GPA00001139253700261
BS-15
Figure GPA00001139253700262
BS-16
BS-17
Figure GPA00001139253700264
But can use various adjuvants to influence the polymerization rate of the deposition inhibitor material of light patternization with photoinitiator system.For example, can use auxiliary or other compound of the chain transfer of reductive agent such as oxygen scavenger or active hydrogen donor to quicken polymerization.Oxygen scavenger claims autoxidator (autoxidizer) again, its can be in the free radical chain process oxygen consumed.The example of available autoxidator has N, the N-dialkyl aniline.Preferred N; the example of N-dialkyl aniline is included in the neighbour; between or the dialkyl aniline that replaced by following group of the one or more positions in the contraposition: methyl; ethyl; isopropyl; the tert-butyl group; 3, the 4-tetramethylene; phenyl; trifluoromethyl; acetyl group; ethoxycarbonyl; carboxyl; the carbonyl acid ester base; the trimethyl silyl methyl; trimethyl silyl; triethylsilyl; trimethyl germyl (germanyl); the triethyl germyl; trimethyl stannyl (stannyl); the triethyl stannyl; n-butoxy; n-pentyloxy; phenoxy group; hydroxyl; acetoxyl group; methyl mercapto; ethylmercapto group; different rosickyite base; sulfo-(sulfydryl); acetylthio; fluorine-based; chloro; bromo and iodo.Can be used for N of the present invention, the representative example of N-dialkyl aniline has 4-cyano group-N, accelerine; 4-acetyl group-N; accelerine; 4-bromo-N, accelerine; 4-(N, N-dimethylamino) benzoic acid ethyl ester; 3-chloro-N; accelerine; 4-chloro-N; accelerine; 3-ethoxy-N, the N xylidin; 4-fluoro-N, accelerine; 4-methyl-N; accelerine; 4-ethoxy-N; accelerine; N, accelerine; N, the N-dimethyl disulfide is for aniline; 4-amino-N; accelerine; the 3-hydroxy-n; accelerine; N, N, N '; N '-tetramethyl-1; the 4-dianiline; 4-acetylaminohydroxyphenylarsonic acid N, accelerine; 2,6-diisopropyl-N; accelerine (DIDMA); 2; 6-diethyl-N, accelerine; N, N; 2; 4,6-pentamethylaminobenzene (PMA) and the right-tert-butyl group-N, accelerine.
Can preferably light trigger be used in combination with the disulfide coinitiator.The example of available disulfide has record in people's such as Davis U.S. Pat 5,230,982.Two kinds of most preferred disulfide are mercaptobenzothiazoler-2-base-disulfide and 6-ethoxy mercaptobenzothiazoler-2-base-disulfide.In addition, the example that can be used as the compound of polymerization accelerator also has mercaptan, thioketones, trihalomethyl compound, lophine dimer compound, salt compounded of iodine, sulfonium salt, azine (azinium) salt, organic peroxide and azide.
But other adjuvants that can add in the described light pattern coating comprise polymer adhesive, filler, pigment, surfactant, bounding force correctives or the like.For ease of being coated on carrier and the functional layer, usually described photocurable film composition is dispersed in and forms solution or slurry in the solvent, liquid is removed in evaporation after applying then (normally by heating).Can adopt for this reason film-forming components is inertia and can be to any solvent of photocurable film addendum.
But but can be preferably in the deposition inhibitor material of described light patternization the light pattern formed material with positive-working implement method of the present invention.For example, the U.S. Pat 4,708,925 (being incorporated herein) of Newman but recorded and narrated the positive-working light pattern composition that contains novolaks phenolics, salt and dye sensitizing agent.In this system, exist between alkaline bleach liquor soluble phenolics and the salt to interact, described interaction produces alkaline-resisting solvent borne when it is poured into a mould film forming.The photodissociation of salt can recover the solubility of resin.With promptly allow to also can only be different by the quinine diazide of sensitization (quinine diazides) a little, salt is easy to use the sensitization of electromagnetic spectrum on a large scale from UV to infrared (280-1100nm).
The example of the compound of known energy sensitization salt has following a few class: the diphenyl-methane that comprises the diphenyl-methane of replacement, xanthene, acridine, methine and polymethine (comprise oxonols (oxonol), cyanine and merocyanine) dyestuff, thiazole, thiazine, azine, amino ketones, porphyrin, coloured aromatics polycyclic hydrocarbon, the aminobenzene vinyl compound of right-replacement, aminotriazyl methane, poly (arylene ether), poly-aryl polyenoid (polyarylpolyene), 2,5-diphenyl isobenzofuran, 2,5-diaryl cyclopentadiene, the diaryl furans, the diaryl thiophene, diaryl pyrrole, poly-aryl phenylene (polyaryl-phenylene), cumarin and poly-aryl-2-pyrazoline.The interpolation of sensitizer in system makes it all responsive to any radiation in the absorption spectrum that falls into described sensitizer.Also has other known positive-working system of one of ordinary skill in the art.
In a preferred embodiment of the inventive method, but the deposition inhibitor material of preferred light patternization is the potpourri of the polymerizable matrix of organosiloxane and energy long UV of quilt or visible radiation triggering.Organosiloxane with to the radiosensitive thermoprene of UV (poly-cis-isoprene), with two-azide (as 2, two (4-nitrine the benzal)-4-methyl cyclohexanones of 6-) but blend be to be used for particularly preferred light pattern composition of the present invention.According to the present invention, these compositions can be randomly to the visible wavelength sensitivity.The people has been arranged, and for example (Applied Optics, 1881135-1136 (1979) have recorded and narrated the sensitization to visible wavelength of poly-cis-isoprene resist that use triplet (triplet) sensitizer such as 9-Fluorenone carry out for J.Frejlich and R.Knoesel.
But can use of the deposition inhibitor material layer exposure of any method easily to light patternization.Described layer can use photomask exposure, also can carry out laser-exposure without photomask.But the importance of step of exposure is the light pattern that the actinic radiation that contains suitable wavelength is provided to light pattern deposition inhibitor layer, but thereby so that desired region is fully exposed the deposition inhibitor material that makes light patternization from solvable become soluble, otherwise or, and other zone keeps initial coating state.
, just can come its development by the known any means in affiliated field in case but light pattern deposition inhibitor layer is exposed.For example, but development can relate to the soluble fraction of removing light pattern deposition inhibitor layer.The method of developing generally includes and is exposed to selective solvent, heat or its combination.Liquid developer can be any appropriate liquid of described photocurable layers that can the uncured zone of selective removal.Can but the light pattern layer after the exposure be sprayed, flushing, scouring, immersion, ultrasonic or otherwise treated, to realize selective removal.Under the simplest situation, but liquid developer can be as the same liquid of solvent when applying the deposition inhibitor material of light patternization.In some cases, but that the deposition inhibitor material of light patternization is not made in the time finally can being removed is soluble, makes that to being exposed to the concrete reaction sensitivity that takes place during the developer solution it is solvable but make then.
Constitute in the Patternized technique of a part of end article at the deposition inhibitor layer of not planning to make light patternization, be used to successfully need to be removed after the patterning zone at it.This removal can realize with the known any means in affiliated field, comprises Cement Composite Treated by Plasma, particularly comprises the plasma of oxygen, based on peeling off and machinery or adhesive means of solvent.
In technology of the present invention, make patterned film process can be lower than 300 ℃ biggest carrier temperature, more preferably be lower than 250 ℃ or even near room temperature (25 ℃-70 ℃) carry out.In case known after the knowledge of the present invention that this paper comprised, temperature selects just to depend on usually carrier well known in the prior art and technological parameter.These temperature are far below traditional integrated circuit and semiconductor machining temperature, and this makes and can use various arbitrarily more cheap carriers relatively, in the flexible polymer carrier.Thus, this technology makes and can make the more cheap significantly improved circuit that contains thin film transistor (TFT) of performance relatively.
In a preferred embodiment, method of the present invention is significantly different with conventional method, has made can adapt on relatively large and base material based on the volume width of cloth and has carried out the film of Thinfilm patternization, and can realize the speed of production that improves.
Method of the present invention randomly makes can be at atmosphere or near operating under the atmospheric pressure and can not operating in sealing or the open environment.
After patterned deposition inhibitor material, comprise various metal inorganic materials or contain the inorganic material of containing metal compound as the functional material of thin film deposition.The metallic compound of this class comprises, for example the negative ion of (according to the periodic table of elements) V family or VI family.This class containing metal compound can, for example, comprise oxide, nitride, sulfide or the phosphide of zinc, aluminium, titanium, hafnium, zirconium or indium, or its combination.Metal comprises, for example, and copper, tungsten, aluminium, nickel, ruthenium or rhodium.
Can use oxide that this technology makes including but not limited to zinc paste (ZnO), aluminium oxide (Al 2O 3), hafnium oxide, zirconia, indium oxide, tin oxide etc.Can use the oxide of the mixed structure of technology manufacturing of the present invention can comprise for example InZnO.Can use the dopant material of technology manufacturing of the present invention can comprise for example ZnO:Al, Mg xZn 1-xO and LiZnO.
Can use the metal of described technology manufacturing to include but not limited to: copper, tungsten, aluminium, nickel, ruthenium and/or rhodium.For one of ordinary skill in the art, obviously also can deposit two kinds, three kinds or more polymetallic alloy, compound can deposit two kinds, three kinds or multicomponent more, and can make the thing such as gradient film and nano-stack.
For the various functional material precursors that can in the ALD thin-film technique, deposit, Handbook of Thin Film Process Technology. the 1st volume that can write referring to Glocker and Shah, Institute of Physics (IOP) Publishing, Philadelphia 1995, related pages B 1.5:1to B 1.5:16 (being incorporated herein); With the Handbook of Thin FilmMaterials that Nalwa writes, the 1st volume, 103-159 page or leaf (being incorporated herein) also comprises the Table V 1.5.1 in the last list of references.
In an embodiment of the inventive method, adopted ALD technology to deposit functional material, but the given area that has applied the deposition inhibitor material of light patternization on the base material is exposed to air-flow less than 500 milliseconds, preferably less than 100 milliseconds.Preferably, base material temperature is lower than 300 ℃ in deposition process, more preferably is lower than 250 ℃.
For example, in concrete an application, we find that each O-M circulates in the layer that forms 1 atomic diameter on 1/4 the treatment surface.Thus, in this case, the conforming layer that forms 1 atomic diameter on treatment surface needs four circulations.Similarly, for forming the conforming layer of 10 atomic diameters, will need 40 circulations.
Embodiment
Explanation to coating unit
All following film embodiment adopt the flow process configuration shown in Fig. 3 and 4.This flow process configuration has pollutes the nitrogen stream 81 that is brought down below 1ppm through purifying with oxygen and water.This gas is transported to some flowmeters by manifold, and the flow of described flowmeter control purge gas and the gas carried by bubbler is with the choice reaction precursor.Except that described nitrogen supply (NS), airflow 90 also is transported to described device.The pre-service of described air process is to remove moisture.
Have with the dirty ALD of being fed to coating unit 10: contain the metal precursor stream 92 that is diluted in the metal precursor in the nitrogen; What contain the nonmetal precursor that is diluted in the nitrogen or oxygenant contains oxidant stream 93; Only the nitrogen purging that is made of this inert gas flows 95.Control the composition of these streams as described below and flow.
Gas bubbler 82 comprises liquid diethyl zinc (DEZ).Flowmeter 85 is transported to described diethyl zinc bubbler 82 with the purity nitrogen air-flow.The output of bubbler 82 comprises now with the saturated nitrogen of corresponding precursor solution.
Gas bubbler 83 comprise liquid dimethyl aluminium isopropoxide (dimethylaluminumisopropoxide, DMAI).Flowmeter 86 is transported to described dimethyl aluminium isopropoxide bubbler 83 with the purity nitrogen air-flow.The output of bubbler 83 comprises now with the saturated nitrogen of corresponding precursor solution.The output stream of DMAI and DEZ bubbler is mixed with the nitrogen dilution stream that transports from flowmeter 87, produce total stream of metal precursor stream 92.In following examples, each stream is as follows:
Flowmeter 85: the stream that leads to the diethyl zinc bubbler
Flowmeter 86: the stream that leads to dimethyl aluminium isopropoxide bubbler
Flowmeter 87: the stream that leads to the metal precursor dilution
Gas bubbler 84 comprises the pure water that is in room temperature.Flowmeter 88 is transported to gas bubbler 84 with the purity nitrogen air-flow, and the saturated vapor logistics is represented in its output.By flowmeter 91 control airflows.With water bubbler output and air logistics with mix from the dilute stream of flowmeter 89, contain total stream of oxidant stream 93 with generation, it has variable water vapour composition, nitrogen composition and total flow.In following examples, each stream is as follows:
Flowmeter 88: lead to the water bubbler
Flowmeter 89: lead to the oxygenant diluent stream
Flowmeter 91: lead to airflow
Flowmeter 94 controls are fed to the flow of the pure nitrogen gas of coating unit.
Logistics or flow 92,93 and 95 and be transported to the atmospheric pressure dispense tip subsequently, they are derived described passage or micro chamber seam at this place as shown in Figure 3.The gap 99 that between passage that extends and base material 97, has about 0.15mm-30 micron.Described micro chamber is about 2.5mm height, and 0.86mm is wide, and the whole length that spreads all over dispense tip is 76mm.In this structure, reactant materials is transported to the centre of described seam, and flows out from front and back.
For depositing, delivery head is set on the part of base material 97, and motion on base material 97 in a reciprocal manner then is shown in arrow 98.Described to-and-fro movement round-robin length is 32mm.This to-and-fro movement round-robin movement rate is 30mm/sec.
The material that uses
(1) Si wafer substrate cuts into 2.5x2.5 " square, in Piranha solution, clean in advance, with distilled water, reagent alcohol flushing and dry.
(2) dimethyl aluminium isopropoxide (can be commercially available) from Strem Chemical Co..
(3) diethyl zinc (can be commercially available) from Aldrich Chemical Co..
DEHESIVE 944 is dimethylsiloxane polymers of the ethenyl blocking that provided by Wacker Chemie AG..Crosslinker V24 is the methylhydrogenpolysi,oxane that is provided by Wacker.Catalyst OL is the organic platinum complex in dimethyl silicone polymer that is provided by Wacker equally.Crosslinker V24 and Catalyst OL are used for additionally solidifying the siloxane polymer such as the DEHESIVE 944 of ethenyl blocking.
950PMMA is the positive-working photoresist based on poly-(methyl methacrylate) that is provided by MicroChem.
HNR-80, Waycoat Negative Resist Developer (WNRD) and OCGRinse 1 obtain from Fujifilm Electronic Materials.HNR-80 is the negative photoresist of UV-sensitivity, comprises as the thermoprene (poly-(cis-isoprene)) of photocrosslinking dispersion of materials in dimethylbenzene and ethyl benzene mixtures.WNRD is the developer that does not contain dimethylbenzene that is used for the polyisopreneyl negative resist, is used as the developer of HNR-80 preparaton.OCGRinse 1 is used as the rinsing liquid of HNR-80 preparaton after development step, and it mainly comprises butyl acetate.
Photosensitivity
But the nominal radiometer reading that uses IL440 photoresist radiometer is estimated the relative photosensitivity of following light pattern coating.
Embodiment 1
Use atmospheric pressure ALD technology to prepare Al 2 O 3 Dielectric layer
This embodiment has recorded and narrated on the Si wafer substrate and has prepared Al 2O 3The layer film coating, it can technology according to the present invention be applied on the deposition inhibitor material of light patternization.In U.S. Patent application US 11/627,525, recorded and narrated in detail and be used to prepare Al 2O 3Equipment with the ZnO layer.Square (62.5mm square) the Si wafer of 2.5X2.5 inch is placed on the platen of this equipment,, and is heated to 200 ℃ with vacuum aided mechanical hook-up fix in position.The platen of the described Si of having base material is placed under the dispense tip of guiding active precursor gas stream.Use micrometer that the spacing between Si wafer substrate and the dispense tip is adjusted to 30 microns.
Dispense tip has the passage of separation, is wherein flowing: the nitrogen of (1) inertia; (2) potpourri of nitrogen, air and water vapour; And the potpourri of (3) active metal alkyl steams (DMAI) in nitrogen.The flow rate of active metal alkyl steam is controlled nitrogen bubble by using independent mass rate control meter by the neat liquid DMAI that is included in the airtight bubbler.Because DMAI vapor pressure at room temperature is lower, so described DMAI bubbler and the delivery line that leads to dispense tip are heated to 60 ℃.The temperature of dispense tip remains on 60 ℃ equally.The bubbling rate that steam rates is overregulated the nitrogen that passes the pure water in the bubbler is controlled.The flow rate adjustment of each gas is arrived the setting shown in the table 1, and for embodiment 1, coating procedure is to start by the period of swing dispense tip on base material with appointment.Final coating is that average thickness is
Figure GPA00001139253700331
The Al of complete uniform deposition 2O 3
Table 1
Sample Layer ??Me 2Al-IOPr?? * ??Et 2Zn Water The N that contains metal alkyl 2Carrier The N that is used for water 2Carrier ??N 2Inert purge Circulation Base material temperature ℃
??1 ??Al 2O 3 ??100 ??0 ??15 ??45 ??90 ??644 ??400 ??200
??2 ??ZnO ??0 ??13 ??15 ??45 ??90 ??644 ??300 ??200
*Flow value, unit are sccm (standard cubic centimeters per minute)
Embodiment 2
Use atmospheric pressure ALD technology to prepare the ZnO semiconductor layer
This embodiment has recorded and narrated preparation ZnO layer film coating on the Si wafer substrate, and it can technology according to the present invention be applied on the deposition inhibitor material of light patternization.Square (62.5mm square) the Si wafer of 2.5X2.5 inch is placed on the platen of ALD equipment,, and is heated to 200 ℃ with vacuum aided mechanical hook-up fix in position.The platen of the described Si of having base material is placed under the dispense tip of guiding active precursor gas stream.Use micrometer that the spacing between Si wafer substrate and the dispense tip is adjusted to 30 microns.
Dispense tip has the passage of separation, is wherein flowing: the nitrogen of (1) inertia; (2) potpourri of nitrogen, air and water vapour; And (3) active metal alkyl steam (diethyl zinc, DEZ) potpourri in nitrogen.The flow rate of active metal alkyl steam is controlled nitrogen bubble by using independent mass rate control meter by the neat liquid DEZ that is included in the airtight bubbler.The bubbling rate that steam rates is overregulated the nitrogen that passes the pure water in the bubbler is controlled.The flow rate adjustment of each gas is arrived the setting shown in the table 1, and for embodiment 2, coating procedure is to start by the period of swing dispense tip on base material with appointment.Final coating is that average thickness is The ZnO of complete uniform deposition.
The comparative example 3
Use of the organosiloxane deposition inhibitor preparation of atmospheric pressure ALD technology by means of light patternization The Al of patterning 2 O 3 Dielectric layer
This embodiment for comparing with technology of the present invention, has described the effectively deposition inhibitor material of light patternization.The Al that has prepared patterning 2O 3Layer film coating (sample 2), is deposited in the zone that the SAD polymkeric substance do not have to cover at its SAD polymeric layer by Si wafer substrate, patterning Thick Al 2O 3Dielectric layer is formed.
Composition is dissolved in A part and the B part solution of preparation Dehesive 944 in the potpourri of toluene and heptane by composition according to appointment in the table 2.The A of equivalent volumes part and B part then, and 10 times of mixture diluted using toluene and heptane (33/48 ratio) are with formation Dehesive944 mother liquor.
Table 2
Composition The A part The B part
Dehesive 944 (30% solid) ??90.0 ??90.0
??Crosslinker?V24 ??0.1 ??0.0
??Catalyst?OL ??0.0 ??3.0
Toluene ??2000.0 ??2000.0
Heptane ??2910.0 ??2910.0
The patterned layer that deposition suppresses polymkeric substance prepares according to following steps:
With the speed spin coating of 3000rpm by 5 parts of 950PMMA solution and 1 part of potpourris that DEHESIVE 944 polysiloxane in toluene/heptane constitute of 0.4% in methyl phenyl ethers anisole/toluene.
2. be after 120-180 ℃ of heating 1-2 minute, in the photomask that under dark UV, sees through the mesh lines pattern in the presence of the nitrogen sample exposure 5-15 minute to coating.
Then with toluene to the exposure sample development 45-90 second, then carry out 3 rinsings.During development step, exposed areas is removed.
The base material that deposition with patterning is suppressed polymeric layer carries out Al then 2O 3Deposition.The Al of patterning 2O 3The preparation of coating is identical with the step of top embodiment 1.Final patterning coating shows as Al 2O 3The grid line pattern of the clear-cut of line.Although deposition is a high selectivity, but the light sensitivity of the deposition inhibitor preparaton of this light patternization is about 3400mJ/cm at 250nm 2, effectively light sensitivity is too low for the patterning coating of reality is made.
The comparative example 4
But do not containing depositing Al on the light pattern coating of siloxane 2 O 3 Layer
This embodiment for comparing with technology of the present invention, but has described the light pattern formed material that does not contain organosiloxane.Half Si wafer is wrapped with adhesive tape, then the HNR-80 photoresist is spun on half of not wrapped.Remove adhesive tape, according to the suggestion of manufacturer to the exposure of photoresist coating with develop.A side of crossing with the adhesive tape bag with the methyl alcohol wiping is to remove adhesive tape remnants (not wiping has applied a side of photoresist).The base material that deposition with patterning is suppressed polymeric layer carries out Al then 2O 3Deposition.The Al of patterning 2O 3The preparation of coating is identical with the step of top embodiment 1.After the deposition, formed average thickness in the not protected side of wafer and be
Figure GPA00001139253700351
Even Al 2O 3Film has deposited on the side that photoresist covers
Figure GPA00001139253700352
Thick Al 2O 3Film.This result shows that described photoresist has only the ability of slight inhibition alumina deposit.For the sake of simplicity, restraint is defined in to be less than or equal to does not have film to be formed on the lip-deep bed thickness of deposition inhibitor at that time basically.The light sensitivity of this photoresist only is～100mJ/cm 2But, compare more much better than the light pattern formed material described in the embodiment 3.But, but the restraint of this light pattern coating only is Too thin for many typical application.
Embodiment 5
Carry out selective deposition with the visible-light curing deposition inhibitor
But prepare light pattern deposition inhibitor coating in the following manner to sensitive to blue light.The solution of light trigger A (following table 3) in methyl phenyl ethers anisole of preparation 0.1%.Preparation contains 1.08%DEHESIVE 944,0.002%Crosslinker V24 and the 0.06% Catalyst OL in the potpourri of 33 parts of toluene and 48 parts of heptane, and the dehesive solution of 0.85g toluene.The mother liquor of solution, 0.24g photoinitiator solution and the 0.85g toluene of TMPTA in toluene of the solution of the polymethylmethacrylate that preparation contains 3.3g 1% in toluene, 0.5g 10%.In this solution, add the described dehesive solution of 0.5g.With this mother liquor of 5g dilution with toluene 1g.With the described solution of speed spin coating of 2000RPM, toasted 1 minute down at 80 ℃, use the blue light exposure and use MIBK to develop, formation negative resist image.But the light sensitivity of this light pattern coating is pact～5mJ/cm 2But comparison is than responsive nearly 3 orders of magnitude of the light pattern formed material described in the embodiment 3.After photosensitive coating is developed, selective deposition aluminum oxide coating layer on the zone of not covered by the deposition inhibitor of described light patternization.The Al of patterning 2O 3The preparation of coating is identical with the step of top embodiment 1.Oval symmetric data shows that the restraint of the deposition inhibitor coating of this light patternization is 500 dusts.
Table 3
Figure GPA00001139253700361
Embodiment 6
Selective deposition Al 2 O 3 But light pattern deposition inhibitor
In this embodiment, but prepared the light pattern coating by the mode identical with embodiment 4, difference is to have added organosiloxane in coating solution, the gained coating is exposed to the UV light pattern, and develops.Selective deposition alumina layer on the deposition inhibitor material of described light patternization.
Preparation contains the dehesive solution of 0.108%DEHESIVE 944,0.0002%Crosslinker V24 and the 0.006% Catalyst OL in the potpourri of 33 parts of toluene and 48 parts of heptane.Preparation contains the coating solution of 1.25g HNR-80,23.75g toluene and the above-mentioned dehesive solution of 0.5g.With the speed spin coating gained solution of 2000RPM 1 minute,,, in WNRD, develop and with OCG Rinse rinsing with UV light exposing patterns 90 ℃ of bakings 1 minute.The base material that deposition with light patternization is suppressed polymeric layer carries out Al then 2O 3Deposition.The Al of patterning 2O 3The preparation of coating is identical with top comparative example's 1 step.Oval symmetric data shows that the restraint of the deposition inhibitor coating of this light patternization is 750 dusts, compares more much better than the result of embodiment 4.
Embodiment 7
But containing deposition ZnO layer on the light pattern coating of siloxane
But press embodiment 6 described step preparation light pattern deposition inhibitor coatings, exposure and development, difference is to have added visible light photoactivated dose of 9-Fluorenone and coating is exposed to the blue light pattern in coating solution.Add the solution of 9-Fluorenone in dimethylbenzene of 0.04g 1% in the coating solution that in 5g embodiment 6, uses.Use the step coating gained solution identical, be exposed to blue light pattern and development with embodiment 6.After photosensitive coating is developed, use coating equipment on the zone of not by the deposition inhibitor of described light patternization being covered the selective deposition Zinc oxide coating identical with comparative example 2.Oval symmetric data shows that but the restraint of light pattern coating C-12 is 850 dusts.

Claims (19)

1. form the method for patterned film, comprising:
(a) provide base material;
(b) but apply the composition of the deposition inhibitor material that comprises light patternization to base material, wherein said deposition inhibitor material includes organic siloxane;
(c) but the deposition inhibitor material of described light patternization is exposed to the imaging actinic radiation to form the pattern that is made of the deposition inhibitor material that is in the second exposure attitude, the wherein said second exposure attitude is different from first and applies attitude;
(d) but the deposition inhibitor material of the light patternization by handling described exposure with described deposition inhibitor patterns of materialization, so that the constituency that does not have described deposition inhibitor material fully to be provided; With
(e) on base material, deposit the functional material layer by gas-phase deposition; Wherein said functional material only is deposited in the constituency that does not have described deposition inhibitor material on the base material basically.
2. the method for claim 1 further is included in the described functional material of deposition and removes described deposition inhibitor material afterwards.
3. the process of claim 1 wherein that described organosiloxane is the polymkeric substance that contains crosslinked ethenyl blocking siloxane.
4. the process of claim 1 wherein that described organosiloxane is to fluoridize or partially fluorinated organosiloxane.
5. the method for claim 1, but wherein said light pattern deposition inhibitor material further comprises the initiator system that is used for the ethylenic addition polymerization, and this initiator system comprises can absorb the imaging actinic radiation to reach the dyestuff of excited state as light trigger.
6. the method for claim 1, but wherein said light pattern deposition inhibitor material is except that including organic siloxane, but the material that further comprises light patternization, but but the material of described light patternization comprise at least a under normal pressure boiling point be higher than the ethylenically unsaturated compounds of 100 ℃ addition polymerization, it is selected from monomer, oligomer or crosslinkable polymkeric substance and composition thereof.
7. the method for claim 6, but the material of wherein said light patternization is polyfunctional acrylate.
8. the method for claim 1, but but wherein said light pattern deposition inhibitor material further comprises the material of the light patternization of the poly-cis-isoprene that contains cyclisation, and with two-azide at the UV radiosensitization, randomly use dye sensitizing agent at the visible wavelength sensitization.
9. the method for claim 1, but but wherein said organosiloxane be light patternization and comprise at least a under normal pressure boiling point be higher than the ethylenically unsaturated compounds of 100 ℃ addition polymerization, it is selected from monomer, oligomer or crosslinkable polymkeric substance and composition thereof.
10. the process of claim 1 wherein that but described light pattern deposition inhibitor material is exposed to the actinic radiation that passes photomask, is not perhaps having to use laser under the situation of photomask.
11. the process of claim 1 wherein that described functional material is metal or comprises metallic compound.
12. the method for claim 11, wherein said metallic compound comprises the negative ion of V family or VI family.
13. the method for claim 11, wherein said metallic compound is oxide, nitride, sulfide or phosphide.
14. the method for claim 11, wherein said metallic compound comprises zinc, aluminium, titanium, hafnium, zirconium and/or indium.
15. the method for claim 11, wherein said metal are copper, tungsten, aluminium, nickel, ruthenium or rhodium.
16. the process of claim 1 wherein that but described light pattern deposition inhibitor material has at least during use
Figure FPA00001139253600021
Restraint.
17. the process of claim 1 wherein that described functional material is by the gas-phase deposition deposition as chemical vapor deposition or atom layer deposition process.
18. the method for claim 17, wherein said atom layer deposition process comprises the ALD of space correlation.
19. the electron device that adopts the method for claim 1 to make, wherein said electron device is selected from integrated circuit, Active Matrix Display, solar cell, active matrix imaging instrument, sensor and rf price, identification or stock's label.
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EP2212747B1 (en) 2015-07-22

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